铂纳米颗粒修饰的多孔卟啉基金属-有机框架化合物高效光催化产氢

通过双溶剂法及其后续的光还原法成功地将2.5 nm 的Pt纳米颗粒嵌入到卟啉基金属-有机框架化合物PCN-222的介孔中（Pt@PCN-222）。该复合材料Pt@PCN-222上的卟啉官能团可以有效地吸收可见光并促进光解水制氢,氢气产量为253 μmol ·g^-1·h^-1。     

高共轭性的四苯基卟啉-Ru(Ⅱ)联吡啶配合物的合成、光学性质及光动力抗癌活性

利用β位吡嗪环共轭连接的卟啉-菲咯啉配体L制备了两亲性的卟啉基-钌(Ⅱ)配合物PorRu和PorZn-Ru,对其进行了核磁及质谱的表征、线性与非线性光谱分析及光动力抗癌活性研究。实验结果显示所得的2个钌配合物具有高的¹O₂量子产率(0.93、0.82)和较高的双光子吸收截面(619、621GM),鼻咽癌HK-1细胞株的摄取量可达每10⁶个细胞约22nmol。体外光动力抗癌活性测试显示在2J·cm^-2的光学剂量及4μmol·L^-1的给药浓度下,抑制效率分别达到(87.44±2.21)%、(45.03±2.85)%。     

Improvement of spectral resolution in the presence of periodic noise and microphonics for hyper-pure germanium detector gamma-ray spectrometry using a new digital filter

The radiation dose of workers and patients resulting from inhaling radon and through the consumption of spring waters was examined in the hospital near the Héviz lake in Hungary. The radiation dose originating from radon was 2.15–3.95 mSv·y⁻¹ concerning workers at the spa. The radiation dose originating from radon in the case of those regularly taking a bath was an average of 0.75 mSv·y⁻¹. Due to the limited duration of treatments a bound effective dose of maximum 100 μSv·y⁻¹ may originate from radon and inhaling radon, while a maximum of 1.4 μSv·y⁻¹ may originate from ingestion of ²²²Rn, ²²⁶Ra, ²³⁴U and ²³⁸U radionuclides.     

一个对2,4,6-三硝基苯酚和Fe3+离子具有双重荧光传感行为的层状镉(Ⅱ)-有机配位聚合物

通过水热法合成了一个由三连接的2,3-喹啉二甲酸桥联扭曲的Cd²⁺八面体形成的二维层状配位聚合物[Cd（QDA）]_n（1）。该配合物发射出较强的蓝色荧光并具有很高的热稳定性和化学稳定性。更为重要的是,该配合物在乙醇分散体系中可快速识别痕量的2,4,6-三硝基苯酚和Fe³⁺离子,其对2,4,6-三硝基苯酚的淬灭常数（K_sv）和检测限（LOD）分别为6.61×10⁴ L·mol^-1和0.83 μmol·L^-1,对Fe³⁺离子的淬灭常数和检测限分别为1.74×10⁴ L·mol^-1和2.70 μmol·L^-1。     

基于金纳米棒刻蚀比色法检测铁、铜离子

采用种子生长法制备金纳米棒(AuNRs)以构建光学传感器,用于Fe³⁺和Cu²⁺的高选择性快速可视化检测。在酸性环境中,Fe³⁺和Cu²⁺通过与KI溶液反应,将I-氧化成I2。I2刻蚀AuNRs,导致其纵向表面等离子体共振(LSPR)吸收峰蓝移,从而实现对Fe³⁺和Cu²⁺的检测。结果表明,反应温度为50℃时,添加0.8 mL 0.1 mol·L^-1 HCl、2 mL AuNRs生长液和20 mmol·L^-1 KI溶液,与2 mL 500 μmol·L^-1 Fe³⁺或30 μmol·L^-1 Cu²⁺反应25或90 min,可将AuNRs刻蚀至LSPR吸收峰消失。该方法对Fe³⁺和Cu²⁺检测具有高选择性和准确性,对于Fe³⁺、Cu²⁺共存体系的检测,可通过加入适量F-与Fe³⁺生成配合物[FeF₆]^3-完成对Fe³⁺的化学掩蔽,消除Fe³⁺的干扰,实现共存体系中Cu²⁺的准确检测。     

2, 6-吡啶二甲酰肼2-羟基萘甲醛酰腙-Cu(Ⅱ)-CopC三元配合物的光谱研究

以2,6-吡啶二甲酸为原料,经酰化、酯化、胺解、亲和加成合成2,6-吡啶二甲酰肼-2-羟基萘甲酰腙(L1)。用紫外-可见吸收光谱、荧光光谱、荧光寿命方法研究了酸碱对L1互变异构的影响及L1、Cu(Ⅱ)、铜运输蛋白(copper trafficking protein,apoCopC)三者的相互结合。结果表明,在pH=7.4、50mmol·L^-1 Tris-HCl缓冲条件下,L1可分别与Cu(Ⅱ)、apoCopC结合形成1:1的配合物,条件结合常数分别为3.32×10⁶mol^-1·L和4.01×10⁵mol^-1·L;而Cu(Ⅱ)-L1与apoCopC结合形成1:1复合物的条件结合常数为8.09×10⁵mol^-1·L。荧光共振能量转移、分子对接模拟表明,L1结合在apoCopC的N端,光谱滴定证实L1、Cu(Ⅱ)、apoCopC可形成以Cu(Ⅱ)为中心的三元配合物。     

2,6-吡啶二甲酰肼2-羟基萘甲醛酰腙-Cu(Ⅱ)-CopC三元配合物的光谱研究

以2,6-吡啶二甲酸为原料,经酰化、酯化、胺解、亲和加成合成2,6-吡啶二甲酰肼-2-羟基萘甲酰腙(L1)。用紫外-可见吸收光谱、荧光光谱、荧光寿命方法研究了酸碱对L1互变异构的影响及L1、Cu(Ⅱ)、铜运输蛋白(copper trafficking protein,apoCopC)三者的相互结合。结果表明,在pH=7.4、50 mmol·L^-1 Tris-HCl缓冲条件下,L1可分别与Cu(Ⅱ)、apoCopC结合形成1:1的配合物,条件结合常数分别为3.32×10⁶ mol^-1·L和4.01×10⁵ mol^-1·L;而Cu(Ⅱ)-L1与apoCopC结合形成1:1复合物的条件结合常数为8.09×10⁵ mol^-1·L。荧光共振能量转移、分子对接模拟表明,L1结合在apoCopC的N端,光谱滴定证实L1、Cu(Ⅱ)、apoCopC可形成以Cu(Ⅱ)为中心的三元配合物。     

基于2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的三个镉/锌配位聚合物的合成、拓扑结构、荧光光谱及DNA作用

以2-（4''-羧基苯基）咪唑-4,5-二羧酸（H₄CPhIDC,C₁₂H₈N₂O₆）为配体,用溶剂热合成了3种配位聚合物{[Cd₂（CPhIDC）（bimb）]·H₂O}_n（1）、{[Cd₂（CPhIDC）（phen）₂]·3H₂O}_n（2）、{[Zn₂（CPhIDC）（bpp）]·1.5H₂O}_n（3）（bimp=1,4-双咪唑基-丁烷,phen=1,10-菲咯啉,bpp=1,3-双（4-吡啶基）-丙烷）。用元素分析、红外光谱、粉末X射线衍射和单晶X射线衍射对配合物进行了表征和结构分析。结构分析表明,主配体以完全去质子化CPhIDC^4-的形式与中心金属离子形成以μ₄和μ₅为配位模式的二维及三维聚合物。配合物1和3是三维网络结构,同时呈现（3,4,5）-连接的（5·6·7）（4·5²·6·7²）（4·5²·6·7⁴·8²）拓扑结构,两者的不同之处是中心离子和辅助配体。配合物2是二维波纹状渔网结构,呈现4⁴·6²拓扑结构,在其空间填充上又类似于DNA双螺旋链的单螺旋结构。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

一种用于活细胞中检测Zn2+的萘酚席夫碱类荧光探针

设计合成了1种基于C=N异构化和螯合荧光增强机理（CHEF）的Zn²⁺荧光探针BMO和NBMO,其结构经¹H NMR,¹³C NMR,¹H-¹H COSY,HSQC,IR和HRMS进行了表征。光谱分析实验结果显示,探针对Zn²⁺均具有较好的选择性和灵敏度,检出限分别为30和21 nmol·L^-1。在0~20 μmol·L^-1浓度的范围内,BMO和NBMO的荧光强度与Zn²⁺浓度可呈良好的线性关系。NBMO-Zn²⁺配合物单晶结构和Job曲线证实该探针与Zn²⁺以1：1配位。NBMO被成功应用于活细胞中Zn²⁺的检测。     

Diffusion of Noble Metals,Zn and Ge in GaSb Single Crystals

Diffusion of Cu, Ag, Au, Ge and Zn in single crystal gallium antimonide has been carried out by measuring Hall effect according to van der Pauw, conductivity, energy dispersive X-ray (EDX) and surface electron microscopy. The best results have been obtained in excess of antimony. The resulting diffusion data in GaSb are diffusivity D_o, activation enthalpy Q, carrier density p and mobility μ at 300 K: Ag: D_o=1.8·10⁻⁴ cm² s⁻¹, Q=1.2 eV, p=6·10¹⁸ cm⁻³, μ=550 cm² (Vs)⁻¹ Au: D_o=6.6·10⁺³ cm² s⁻¹, Q=2.7 eV, p=5·10¹⁸ cm⁻³, μ=500 cm² (Vs)⁻¹ Cu: D_o=3.2·10⁺⁸ cm² s⁻¹, Q=2.7 eV, p=2·10¹⁸ cm⁻³, μ=150 cm² (Vs)⁻¹ Zn: D_o=9.2·10⁻² cm² s⁻¹, Q=1.8 eV, p=2·10²⁰ cm⁻³, μ=80 cm² (Vs)⁻¹ Ge: D_o=1.0·10⁻¹ cm² s⁻¹, Q=1.7 eV, p=1·10¹⁹ cm⁻³, μ=320 cm² (Vs)⁻¹. This revised version was published online in August 2006 with corrections to the Cover Date.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.